TW201714940A - Rubber composition and tire - Google Patents

Abstract

A rubber composition including an aminoguanidine derivative (A), a natural rubber and/or a synthetic rubber (B), an inorganic filler (C), a silane coupling agent (D), and zinc phosphate (E).

Description

Rubber composition and tire

The present invention relates to a rubber composition and a tire containing the rubber composition.

The filler is mixed with rubber, and is blended based on the reinforcement, increment, or special function of the rubber. The carbon black which is a typical filler contributes not only to the improvement of the mechanical properties such as the elastic modulus and the breaking strength of the rubber (the reinforcing effect) but also to the conductivity.

A method of obtaining a rubber composition which is similar to carbon black and having a low heat build-up property, that is, a low-loss rubber composition, is known as a method of using an inorganic filler such as cerium oxide, and has been applied to a consideration of the environment. The low-cost fuel tire is a rubber composition of the object.

The rubber composition of the inorganic filler is blended. When the inorganic filler is blended, the inorganic filler, especially the hydrophilic cerium oxide having a sterol group on the surface, has low affinity with the hydrophobic rubber, and is composed of rubber. Since the substance is agglomerated, in order to improve the reinforcing property by cerium oxide and to obtain a low heat generating effect, it is necessary to improve the affinity of cerium oxide and rubber. In the method, a synthetic rubber which is subjected to terminal modification by a polar group to improve affinity with an inorganic filler is known (see Patent Document 1), and a monomer having a polar group is copolymerized to improve affinity with an inorganic filler. Synthetic rubber (see Patent Document 2) and the like. A method of modifying a natural rubber and introducing it into a polar group is known as a method of modifying a natural rubber by oxidizing a ruthenium compound having a polar group (see Patent Document 3), and by including a modified polar group. A method of adding a decane coupling agent to the rubber composition of the natural rubber and the cerium oxide to further improve the dispersibility of cerium oxide (refer to Patent Document 4).

As described above, studies have been conducted to improve the dispersibility of cerium oxide, and since cerium oxide is acidic, research on suppressing the vulcanization retardation due to adsorption of cerium oxide by a vulcanization accelerator has been conducted. For example, in Patent Document 5, by suppressing the vulcanization delay by adding polyethylene glycol or an amine. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2011-108009 (Patent Document 3) JP-A-2009-108204 (Patent Document 4) JP-A-2011-246513 No. [Patent Document 5] Japanese Special Report 2001-139727

[Problems to be Solved by the Invention] However, since polyethylene glycol and an amine have side effects of shortening the molding time, there is also a problem that workability is lowered.

It is expected that the future world will pay more and more attention to the environmental problems such as carbon dioxide concentration and air pollution in the atmosphere. It is necessary to provide an inorganic filler such as cerium oxide, which will not reduce the productivity and suppress the rotational resistance of the tire. A rubber composition and a tire technology which are excellent in low fuel cost and low in fuel cost.

The present invention has been made in view of the above problems, and an object thereof is to provide a rubber composition which is a rubber composition containing an inorganic filler, which is excellent in low loss and breaking strength, and which ensures both the molding time and the shortening of the vulcanization time. And providing a tire containing the rubber composition. [Means for solving the problem]

The inventors of the present invention have conducted an effort to find a rubber composition obtained by mixing zinc phosphate, an amine hydrazine derivative, a natural rubber and/or a synthetic rubber, a filler containing an inorganic filler, and a decane coupling agent. The above problems can be solved, and the present invention is finally completed.

That is, the present invention is as follows. [1] A rubber composition comprising: an amine hydrazine derivative (A), a natural rubber and/or a synthetic rubber (B), an inorganic filler (C), a decane coupling agent (D), and zinc phosphate (E) ). [2] The rubber composition according to [1], wherein the inorganic filler (C) contains cerium oxide. [3] The rubber composition of [1] or [2], wherein the inorganic filler (C) contains carbon black. [4] The rubber composition according to any one of [1] to [3], wherein the amine hydrazine derivative (A), the natural rubber, and/or the synthetic rubber (B), the inorganic filler ( C), the decane coupling agent (D) and the zinc phosphate (E) are mixed at 20 to 180 ° C. [5] The rubber composition according to any one of [1] to [4] wherein the content of the zinc phosphate (E) is 0.01 to 10 parts by mass based on 100 parts by mass of the natural rubber and/or the synthetic rubber (B). Parts by mass. [6] The rubber composition according to any one of [1] to [5] wherein the content of the amine hydrazine derivative (A) is 100 parts by mass relative to the natural rubber and/or the synthetic rubber (B) It is 0.01 to 10 parts by mass. [7] A tire comprising the rubber composition according to any one of [1] to [6] on the tread. [Effects of the Invention]

According to the present invention, it is possible to provide a rubber composition which is a rubber composition containing an inorganic filler, which is excellent in low loss and breaking strength, and which ensures both the formation time and the shortening of the vulcanization time; and the rubber composition can be provided. Tires.

In the following, the embodiments of the present invention (hereinafter referred to as "the present embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from the scope of the invention.

[Rubber composition] The rubber composition of the present embodiment contains an amine-based hydrazine derivative (A), a natural rubber, and/or a synthetic rubber (B) (hereinafter, simply referred to as "rubber component (B)"). Filler (C), decane coupling agent (D), and zinc phosphate (E).

[Amine hydrazine derivative (A)] The amine hydrazine derivative (A) is not particularly limited, and for example, an amine hydrazine, a diamino hydrazine, a triamine hydrazine or the like, and the like can be used.

The amino hydrazine derivative (A) exhibits strong basicity due to the fact that the positive charge of its conjugate acid is dispersed and stabilized by a majority of nitrogen atoms present in its molecule, usually in the form of a complex with a acid (salt). presence.

The amine sulfonium salt is not particularly limited, and, for example, an amine sulfonium carbonate, an amine hydrazine hydrochloride, an amine hydrazine hydrate, an amino hydrazine hydrobromide, an amine sulfonium hemisulfate, an amine group can be exemplified.胍Nitrate, amino oxalate, amine bismuth phosphate, amine hydrazine acetate, amine decyl sulfonate, amine hydrazine perchlorate, amine ruthenate, amino bismuth borate Salt, amino phenyl phosphinate, and the like.

The diamino sulfonium salt is not particularly limited, and, for example, diamino sulfonium carbonate, diamine hydrazine hydrochloride, diamino hydrazine iodate, diamino hydrazine hydrobromide, diamine hydrazine can be exemplified. Hemisulfate, diamine sulfonium nitrate, diamino valerate, diamine sulfonium phosphate, diamino hydrazine acetate, diamine decyl sulfonate, diamine hydrazine perchlorate , diamino decanoate, diamino sulfonium borate, diamino phenyl phosphinate, and the like.

The triamine sulfonium salt is not particularly limited, and, for example, triamine sulfonium carbonate, triamine hydrazine hydrochloride, triamine hydrazine iodate, triamine hydrazine hydrobromide, triamine hydrazine can be exemplified. Hemisulfate, triamine sulfonium nitrate, triamine valerate, triamine sulfonium phosphate, triamine hydrazine acetate, triamine decyl sulfonate, triamine hydrazine perchlorate And a triamine decanoate, a triamine sulfonium borate, a triamine phenyl phosphinate, and the like.

Among these amino-based hydrazine derivatives, from the viewpoint of easiness of availability, it is preferred to use an amine hydrazine or a salt thereof, and it is more preferable to use an amine hydrazine carbonate or an amine hydrazine hydrochloride from the viewpoint of economy.

By reacting the hydrazine moiety contained in the above amine hydrazine derivative (A) with the rubber component (B), the polar group is introduced into the rubber component (B), and the polar group of the rubber component (B) is introduced. The affinity of the polar filler (C) which the inorganic filler (C) can have (especially the ruthenium group on the surface of the cerium oxide) is improved, so the adhesion between the rubber component (B) and the inorganic filler (C) Sexual improvement. Further, the rubber molded body such as a tire obtained by using the rubber composition of the present embodiment is excellent in low loss.

It is known that the rubber composition obtained by separately adding the above-mentioned zinc phosphate or the above-described amine ruthenium derivative can also obtain the effect of ensuring sufficient molding time and shortening the vulcanization time in the present embodiment, but the effect is more remarkable when used in combination. Although the reason is not clear, it is speculated that it may be a complex formed by the reaction of zinc phosphate and an amine hydrazine derivative in the mixture, and the cerium oxide or zinc oxide is more than the zinc phosphate or the amine hydrazine derivative alone. The state of dispersion has changed dramatically.

The amine hydrazine derivative (A) can be obtained by a known method, and for example, an arbitrary salt can be obtained by an exchange reaction of a salt or the like.

The content of the amine hydrazine derivative (A) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, still more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the rubber component (B). By setting the content of the amine hydrazine derivative (A) within the above range, a small amount of a polar group (a group derived from the amine hydrazine derivative (A)) can be uniformly introduced into the double bond site which the rubber component (B) can have. And the amine hydrazine derivative (A) has a tendency to react with zinc phosphate (B). Thereby, the workability of the rubber composition is further improved, and the affinity between the rubber component (B) and the inorganic filler (C) or zinc oxide is further improved, and the obtained rubber molded article tends to be more excellent in low loss. Further, there is a tendency to ensure sufficient molding time and shorten the vulcanization time.

[Rubber component (B)] The rubber component (B) can be obtained by using natural rubber obtained from rubber trees and/or synthetic rubber obtained by industrial production from petroleum or the like. Further, since the natural rubber has high tearing efficiency and excellent fatigue resistance, the synthetic rubber is excellent in abrasion resistance, and therefore, it is possible to arbitrarily mix the two rubber types according to the purpose. Further, in the present embodiment, at least a part of the aminoguanidine derivative (A) may be bonded to at least a part of the rubber component (B) by a covalent bond or a non-covalent bond.

(Natural Rubber) The natural rubber is not particularly limited. For example, any of the natural rubber latex, the sheet rubber obtained by solidifying and drying the natural rubber latex, and the block rubber may be used as a raw material. The main component of natural rubber can be exemplified by polyisoprene.

The sheet-like rubber is not particularly limited, and for example, it can be exemplified as "the international quality packaging standard for various grades of natural rubber" (commonly known as the Green Paper). More specifically, the film is dried by smoking, and the film is dried by hot air drying (ADS), and the coagulum is sufficiently washed with water and dried by hot air. And it is obtained from Crepe, TC rubber (Technical Classified Rubber), SP Rubber (Super Processing Rubber), MG rubber, PP silicone rubber, rubber added with a softener, a peptizer, and the like.

The block rubber is not particularly limited, and examples thereof include Standard Malaysian Rubber (SMR) made in Malaysia, Standard Indonesian Rubber (SIR) made in Indonesia, Standard Thai Rubber (STR) made in Thailand, and Sri Lanka Rubber (SLR) made in Sri Lanka. Singapore Singapore Rubber (SSR), Vietnam's Standard Vietnamese Rubber (SVR), India's Indian Standard Natural Rubber (ISNR), and China's Standard China Rubber (SCR).

Further, a rubber obtained by oxidizing a natural rubber latex and solidifying it may be used, and oxidation of the natural rubber latex can be carried out by a known method. For example, the natural rubber latex can be oxidized by air-oxidation of a natural rubber latex dissolved in an organic solvent at a ratio of 1 to 30% by mass in the presence of a metal-based oxidation catalyst according to Japanese Patent Application Laid-Open No. Hei 8-81505. . Further, as described in JP-A-H09-136903, a carbonyl compound is added to the natural rubber latex to be oxidized. In the case of the oxidation of air, as described in Japanese Laid-Open Patent Publication No. Hei 9-136903, air oxidation can be carried out in the presence of a radical generating agent in order to promote air oxidation. As the radical generator, for example, a peroxide radical generator, a redox radical generator, an azo radical generator, or the like can be suitably used.

These natural rubber raw materials may be used alone or in combination of two or more.

(Synthetic rubber) The synthetic rubber is not particularly limited, and examples thereof include, for example, 1,4-polybutadiene, 1,2-polybutadiene, 1,4-polyisoprene, and 3,4-polyisoprene. Arene, isobutylene rubber, isoprene-isobutylene rubber, styrene-butadiene rubber, styrene-isoprene rubber, terminal modified styrene-butadiene rubber, chloroprene rubber, nitrile rubber A diene rubber having a double bond in a molecule such as an ethylene-propylene rubber, a propylene-butene rubber, or an ethylene-propylene-diene rubber.

The content of the rubber component (B) is preferably from 35 to 80% by mass, more preferably from 40 to 70% by mass, even more preferably from 40 to 60% by mass, based on the total amount of the rubber composition. When the content of the rubber component (B) is within the above range, the low loss property and the breaking strength tend to be more excellent.

[Inorganic filler (C)] The inorganic filler (C) is not particularly limited as long as it is an inorganic filler used in the technical field, and for example, at least one selected from the group consisting of ruthenium, a typical metal, or a transition metal can be exemplified. An oxide; a hydroxide of a typical metal or a transition metal; a hydrate thereof; a carbonate of a cerium, a typical metal or a transition metal; and carbon black.

Moreover, the inorganic filler (C) can also be classified into a reinforcing filler used for the purpose of improving the reinforcing property, and a non-reinforcing filler used for the purpose of increasing or improving the workability such as the rolling property and the extrusion property.

The reinforcing filler is not particularly limited, and examples thereof include ceria, surface-treated clay, carbon black, mica, calcium carbonate, aluminum hydroxide, aluminum oxide, titanium oxide, and the like which are active on the surface.

Further, the non-reinforcing filler is not particularly limited, and examples thereof include calcium carbonate, clay, talc, diatomaceous earth, pulverized quartz, fused silica, aluminosilicate, organic acid surface-treated calcium carbonate, magnesium carbonate, zinc carbonate, and cesium. Calcium acid, iron (III) oxide, and the like.

Among the above, the reinforcing filler is preferred, and cerium oxide and carbon black are more preferable. When such an inorganic filler (C) is used, the reinforcing property of the rubber composition is further improved, and at the same time, the affinity between the rubber component (B) and the inorganic filler (C) is further improved, and the rubber molded body obtained has a low loss tendency. More excellent.

Further, the cerium oxide is not particularly limited, and for example, wet cerium oxide (aqueous ceric acid) or dry cerium oxide (anhydrous ceric acid) or the like can be used. Further, the BET specific surface area of the cerium oxide is preferably from 40 to 350 m ² /g, more preferably from 100 to 300 m ² /g, still more preferably from 150 to 250 m ² /g. When the BET surface area of cerium oxide is in the above range, the particle diameter of cerium oxide becomes appropriate, the tensile strength is further improved, and the hysteresis loss tends to be lowered.

Further, the carbon black is not particularly limited, and examples thereof include General Purpose Furnace (GPF), Fast Extruding Furnace (FEF), Semi-Reinforcing Furnace (SRF), High Abrasion Furnace (HAF), Intermediate Super Abrasion Furnace (ISAF), and Super Abrasion. Furnace (SAF) grades, etc.

The content of the inorganic filler (C) is preferably 5 to 120 parts by mass, more preferably 20 to 100 parts by mass, still more preferably 30 to 100 parts by mass, per 100 parts by mass of the organic component of the rubber composition. When the content of the inorganic filler (C) is within the above range, the workability and the reinforcing property of the rubber composition are further improved, and the obtained rubber molded article tends to be more excellent in low loss. Here, the term "organic component of the rubber composition" means an amine hydrazine derivative (A), a rubber component (B), a decane coupling agent (D), and other organic components.

[Hydrane coupling agent (D)] The decane coupling agent (D) is not particularly limited, and examples thereof include bis(3-triethoxydecylpropyl) tetrasulfide and bis(3-trimethoxyfluorene). Propyl) tetrasulfide, bis(3-methyldimethoxydecylpropyl) tetrasulfide, bis(2-triethoxydecylethyl)tetrasulfide, bis(3-triethyl) Oxylylpropyl) disulfide, bis(3-trimethoxydecylpropyl) disulfide, bis(3-triethoxydecylpropyl)trisulfide, 3-trimethoxyanthracene propyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxydecylpropylbenzothiazolyl tetrasulfide, 3-trimethoxydecylpropylmethacrylate Sulfide-based decane coupling agent such as monosulfide; 3-hexylthiopropyltriethoxydecane, 3-octylthiopropyltriethoxydecane, 3-mercaptothiopropyltriethoxylate Base decane, 3-lauryl thiopropyltriethoxy decane, 2-hexyl thioethyl triethoxy decane, 2-octyl thioethyl triethoxy decane, 2-mercaptothio ethane Triethoxy decane, 2-lauryl thioethyl triethoxy decane, 3-hexyl thiopropyl trimethoxy decane, 3- octyl Thiopropyltrimethoxydecane, 3-mercaptothiopropyltrimethoxydecane, 3-laurylthiopropyltrimethoxydecane, 2-hexylthioethyltrimethoxydecane, 2- a sulfur-based decane coupling agent such as octylthioethyltrimethoxydecane, 2-mercaptothioethyltrimethoxydecane, 2-lauroylthioethyltrimethoxydecane; 3-mercaptopropyltrimethoxy A fluorenyl decane coupling agent such as decane, 3-mercaptopropyltriethoxy decane or 3-mercaptopropylmethyldimethoxydecane; 3-aminopropyltrimethoxydecane, 3-aminopropyl An amine decane decane coupling agent such as triethoxy decane; an epoxy decane system such as γ-glycidoxypropyltrimethoxydecane or γ-glycidoxypropylmethyldiethoxydecane a decane coupling agent or the like.

Among them, a thioether decane coupling agent is preferred. When such a decane coupling agent (D) is used, the affinity between the rubber component (B) and the inorganic filler (C) tends to be improved.

The content of the decane coupling agent (D) is preferably from 1 to 20 parts by mass, more preferably from 3 to 15 parts by mass, still more preferably from 6 to 10 parts by mass, per 100 parts by mass of the inorganic filler (C). When the content of the decane coupling agent (D) is within the above range, the affinity between the rubber component (B) and the inorganic filler (C) tends to be improved.

[Zinc Phosphate (E)] Zinc phosphate (E) is a compound represented by the chemical formula Zn ₃ (PO ₄ ) ₂ or Zn ₂ P ₂ O ₇ . Among them, a compound represented by the chemical formula Zn ₃ (PO ₄ ) ₂ is preferably used, and any of an anhydride and a hydrate can be used. Zinc phosphate (E), for example, zinc phosphate tetrahydrate (Zn ₃ (PO ₄ ) ₂ ‧4H ₂ O) and zinc diphosphate (Zn ₃ (PO) manufactured by Wako Pure Chemical Industries, Ltd., in the form of a commercially available product ₄ ) ₂ ) etc.

The content of the zinc phosphate (E) is preferably 0.01 to 10 parts by mass, more preferably 1 to 7.5 parts by mass, still more preferably 2 to 5 parts by mass, per 100 parts by mass of the rubber component (B). In addition, when the content of the zinc atom (Zn) itself is converted, the content of the zinc phosphate (E) is preferably 0.1 to 8 parts by mass, more preferably 0.3 to 5 parts by mass, per 100 parts by mass of the rubber component (B). More preferably, it is 0.5 to 3 parts by mass. When the content of the zinc phosphate (E) is within the above range, it tends to be less likely to affect the vulcanization behavior of the rubber composition.

[Other Components] In addition to the above components, the rubber composition of the present embodiment may contain a blending agent which is generally used in the rubber industry as needed. Such a blending agent is not particularly limited, and examples thereof include an anti-aging agent, a softening agent, a vulcanization accelerator, a vulcanization accelerating aid, a vulcanizing agent, and the like. Commercially available products can be suitably used as such a blending agent.

(Anti-aging agent) The anti-aging agent is not particularly limited, and examples thereof include a naphthylamine compound, a p-phenylenediamine compound, a hydroquinone derivative, a bis, a ginseng, a polyphenol compound, a diphenylamine compound, and a quinine. A porphyrin compound, a monophenol compound, a thiobisphenol compound, a hindered phenol compound, or the like. Among them, from the viewpoint of further anti-aging effects, an amine-based anti-aging agent is preferred, and a p-phenylenediamine-based compound or a diphenylamine-based compound is more preferable.

The diphenylamine-based compound is not particularly limited, and examples thereof include 4,4'-(α-methylbenzyl)diphenylamine, 4,4'-(α,α-dimethylbenzyl)diphenylamine, and p-pairs. Toluenesulfonyl decylamine) diphenylamine, 4,4'-dioctyldiphenylamine, etc.; among them, 4,4'-(α-methylbenzyl)diphenylamine is the most effective in terms of anti-aging effect. good.

Further, the p-phenylenediamine-based compound is not particularly limited, and examples thereof include N,N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, and N,N. '-Di-2-naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-phenyl-N'-(3-methylpropenyloxy-2- Hydroxypropyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-benzene Diamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-benzene Diamines and the like; among these, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine is preferred from the viewpoint of higher anti-aging effect and cost.

The content of the anti-aging agent is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the rubber component (B).

(Softener) The softener is not particularly limited, and examples thereof include mineral oil-based softeners derived from petroleum and coal tar, vegetable oil-based softeners derived from fatty oils and pine trees, and synthetic resin-based softeners. These softeners may be used alone or in combination of two or more.

(vulcanization accelerator) The vulcanization accelerator is not particularly limited, and examples thereof include thiazole compounds such as mercaptobenzothiazole and di-2-benzothiazolyl disulfide; and N-cyclohexyl-2-benzothiazolylsulfenic acid; a sulfenamide compound such as decylamine, N,N'-dicyclohexyl-2-benzothiazolylsulfenylamine or N'-t-butyl-2-benzothiazolylsulfenamide; An anthraquinone compound such as phenylhydrazine. These vulcanization accelerators may be used alone or in combination of two or more.

The content of the vulcanization accelerator is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the rubber component (B).

(Vulcanization Promoting Aid) Further, in the present embodiment, in order to further enhance the effect of the vulcanization accelerator, it is preferred to use a vulcanization accelerating aid. The vulcanization accelerating aid is not particularly limited, and examples thereof include zinc compounds such as zinc oxide and higher fatty acids such as stearic acid. Among them, zinc oxide is preferred, and those obtained by surface treatment with an amine-based dispersant or a wetting agent may also be used.

Since zinc phosphate (E) functions as a vulcanization accelerating aid similarly to zinc oxide, when zinc oxide is used as a zinc source, for example, the total content of zinc oxide and zinc phosphate is preferably 100 parts by mass based on 100 parts by mass of the rubber component (B). 0.01 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, still more preferably 1 to 5 parts by mass.

The content of the zinc oxide is preferably 0.01 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, still more preferably 0.8 to 5 parts by mass, per 100 parts by mass of the rubber component (B). In addition, the content of the zinc oxide is preferably from 0.008 to 8 parts by mass, more preferably from 0.1 to 5 parts by mass, even more preferably from 0.1 to 5 parts by mass, based on 100 parts by mass of the rubber component (B). 0.5 to 3 parts by mass. When the content of the zinc oxide is within the above range, the properties such as the molding time and the tensile strength of the rubber composition tend to be highly balanced.

(Vulcanizing Agent) The vulcanizing agent is not particularly limited as long as it is generally used in the technical field, and examples thereof include sulfur and peroxide. Among them, sulfur is preferred.

The content of the vulcanizing agent is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the rubber component (B). When the content of the vulcanizing agent is 0.1 part by mass or more, vulcanization proceeds sufficiently. When the content of the vulcanizing agent is 5 parts by mass or less, the so-called scorch time increases, and it tends to suppress the coking of the rubber during kneading.

The rubber composition of the present embodiment preferably has an amine hydrazine derivative (A), a rubber component (B), an inorganic filler (C), a decane coupling agent (D), and zinc phosphate (E) in 20~. Mixed at 180 ° C. The mixing temperature is preferably from 20 to 180 ° C, more preferably from 50 to 160 ° C, still more preferably from 80 to 160 ° C. Such a rubber composition can suppress the decomposition of the amine-based hydrazine derivative (A), and the reaction tendency of the amine hydrazine derivative (A) with respect to the rubber component (B) can be more appropriately performed. Therefore, the affinity between the rubber component (B) and the inorganic filler (C) is further improved, and the obtained rubber molded article tends to be more excellent in low loss.

[Method for Producing Rubber Composition] Next, a method for producing the rubber composition of the present embodiment will be described. The method for producing the rubber composition of the present embodiment is to mix the amine hydrazine derivative (A), the rubber component (B), the inorganic filler (C), the decane coupling agent (D), and the zinc phosphate (E). The method can be any, and is not particularly limited.

When mixing, a mixer, an extruder, a kneading machine, or the like can be used. Among them, from the viewpoint of improving dispersibility, it is preferred to carry out mixing by a kneading machine. The method of adding the amine hydrazine derivative (A) and the zinc phosphate (E) to a mixer, an extruder, a kneader or the like is not particularly limited. For example, a method of directly adding a powder and dissolving it in a solvent are used. The method in which the solution is further added, and the method of adding it in the form of an emulsion.

The mixing temperature is preferably from 20 to 180 ° C, more preferably from 50 to 160 ° C, still more preferably from 80 to 160 ° C. When the mixing temperature is 20 to 180 ° C, the rubber component (B) and the amine hydrazine derivative (A), and the zinc phosphate (E) and the amine hydrazine derivative (A) can be more homogeneously mixed. The reaction proceeds more appropriately, and tends to further inhibit the thermal decomposition of the aminoguanidine derivative (A).

The mixing time is preferably from 0.5 to 30 minutes, more preferably from 2 to 10 minutes, and even more preferably from 2 to 7 minutes. When the kneading time is 0.5 to 30 minutes, it tends to maintain productivity and sufficiently react the rubber component (B) with the amine hydrazine derivative (A) and the zinc phosphate (E) with the amino hydrazine derivative (A).

The reaction environment is preferably carried out in the presence of oxygen such as air. Oxygen has a tendency to promote the radical reaction of the rubber component (B) with the amine hydrazine derivative (A).

For the purpose of adjusting the reactivity of the amine-based fluorene derivative (A), a polymerization initiation (reaction promoting) agent or a polymerization inhibition (reaction retardation) agent can be used. The polymerization initiator may, for example, be benzamidine peroxide, hydrogen peroxide, cumene hydroperoxide, t-butyl hydroperoxide, di-tert-butyl peroxide, 2,2-azodiiso Butyronitrile, 2,2-azobis(2-diaminopropane) hydrochloride, 2,2-azobis(2-diaminopropane) dihydrochloride, 2,2-azobis ( 2,4-Dimethylvaleronitrile), potassium persulfate, sodium persulfate, ammonium persulfate, and the like. Further, in order to lower the reaction temperature, a redox-based polymerization initiator is preferably used. The reducing agent to be combined with the peroxide in the redox polymerization initiator may, for example, be tetraethylenepentamine, thiol, acid sodium sulfite, reducing metal ion, ascorbic acid or the like. These may be used alone or in combination of two or more.

The polymerization inhibitor may, for example, be a diphenyl picryl hydrazyl, a galvanoxyl, a verdazyl, or the like, or a stable radical substance such as an enzyme or a phenol derivative. A benzopyrene derivative or a nitro compound is easily added to a radical to form a stable radical. These may be used alone or in combination of two or more.

[Tire] The tire of the present embodiment contains the rubber composition described above, and it is particularly preferable that the tread contains the rubber composition. Thereby, the tire of this embodiment is excellent in low fuel cost. The method for producing a tire according to the present embodiment is not particularly limited as long as it is produced by containing the rubber composition, and can be produced by a usual method. Further, the gas filled in the tire may be a passive gas such as nitrogen gas, argon gas or helium gas in addition to the air which is usually or adjusted by oxygen partial pressure. [Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples below.

[Example 1] According to the composition of Table 1, a natural rubber solidified body (trade name "RSS #1", manufactured by Kato Co., Ltd.), cerium oxide was initially used as LABO PLASTOMILL (manufactured by Toyo Seiki Seisakusho Co., Ltd.). (trade name "Nipsil AQ", manufactured by Tosoh dioxin (manufactured by Tosoh Corp.), BET surface area = 207 m ² /g), decane coupling agent (bis(3-triethoxydecylpropyl) tetrasulfide, EVONIK JAPAN (manufactured by the company), zinc oxide (manufactured by Wako Pure Chemical Industries, Ltd.), zinc phosphate tetrahydrate (Zn ₃ (PO ₄ ) ₂ ‧4H ₂ O, and Wako Pure Chemical Industries, Ltd.), hard Fatty acid (manufactured by Wako Pure Chemical Industries, Ltd.) and amino sulfonium carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) were kneaded at 145 ° C for 5 minutes. Then, the obtained kneaded product was cooled to 55 ° C, and sulfur (250 μm, manufactured by Hosei Chemical Industry Co., Ltd.) and CBS (N-cyclohexyl-2-benzothiazolylsulfenamide) as a vulcanization accelerator were introduced thereto. , Wako Pure Chemical Industries Co., Ltd.) and DPG (diphenyl fluorene, Wako Pure Chemical Industries, Ltd.) were kneaded at 90 ° C for 3 minutes to prepare an unvulcanized rubber composition.

Then, a vulcanized rubber composition was obtained by using a press (manufactured by Kitagawa Seiki Co., Ltd.) at a temperature of 145 ° C and 10 MPa under conditions of 1.5 times the t90 値 (minutes) for 19 to 40 minutes. T90 is the time until the evaluation by the vulcanization tester is reached (90% of the difference between the maximum and minimum torque of the torque + minimum 値).

[Comparative Example 1] The same as in Example 1, except that the amount of zinc oxide used was changed without using the amine sulfonium carbonate and the zinc phosphate tetrahydrate, and the number of moles of zinc atoms was the same as in Example 1. The operation is to prepare an unvulcanized rubber composition, and a vulcanized rubber composition is obtained.

Using the obtained vulcanized rubber composition, the heat build-up and tensile breaking strength were measured and evaluated by the following methods. The results are shown in Table 1.

(1) Heat generation The loss of tangent (tan δ) was measured on the vulcanized rubber composition using a dynamic viscoelasticity measuring apparatus (DMS6100 manufactured by Seiko Instruments Co., Ltd.) at a temperature of 50 ° C, a strain of 0.05%, and a frequency of 10 Hz, and the comparison of Table 1 was made. Example 1 is 100 to express the index. The smaller the index 値, the lower the tan δ, indicating that the rubber composition is less heat-generating.

(2) Tensile breaking strength The above-mentioned vulcanized rubber composition was subjected to a tensile test in accordance with JIS K6251:2010, and the tensile breaking strength was measured, and the index of Comparative Example 1 of Table 1 was 100. The larger the index 値, the greater the tensile strength at break.

(3) Forming time/vulcanization time The molding time (3-1) and the vulcanization time (3-2) shown below were measured, and the ratio of the forming time to the vulcanization time (forming time/vulcanization time) was determined. In Comparative Example 1, the index was 100 to express the index. The larger the index 値, the more the formation time is ensured and the curing time is shortened.

(3-1) Forming time For the above-mentioned unvulcanized rubber composition, a vulcanization tester (Rotorless Rheometer RLR-4 manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used, and according to JIS K 6300-2:2001 mold vulcanization test A method, at a temperature of 145 T10 was measured at °C, amplitude angle ±1°, and vibration number 100 cpm. The time until t10 is reached (10% of the difference between the maximum and minimum torque of the torque + the minimum 値) can be used as the length of the flow time during vulcanization molding, that is, as an index of workability or molding time. The longer this time, the more excellent the formability.

(3-2) Vulcanization time For the above unvulcanized rubber composition, a vulcanization tester (Rotorless Rheometer RLR-4 manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used, and according to JIS K 6300-2:2001 mold vulcanization test A method, at a temperature of 145 T90 was measured at °C, amplitude angle ±1°, and vibration number 100 cpm. T90 is the time to reach (90% of the difference between the maximum and minimum torque of the torque + the minimum 値), and can be used as an indicator of the vulcanization time. The shorter this time, the more excellent the productivity.

[Table 1] In Table 1, each component of the blending formula represents a mass part, and ( ) represents a mass part converted into a zinc atom.

As is clear from Table 1, the rubber composition obtained by mixing an amine bismuth phosphate, a natural rubber, a cerium oxide, and a decane coupling agent is excellent in low heat build-up, and has a large tensile strength at break, and further sufficient shape can be ensured. Time and shorten the curing time.

The present application is based on a Japanese patent application filed on Sep. 4, 2015, the disclosure of which is hereby incorporated by reference. [Industrial use]

The rubber composition of the present invention has industrial applicability as a material of a tire or the like.

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Claims (7)

A rubber composition comprising: an amine hydrazine derivative (A), a natural rubber and/or a synthetic rubber (B), an inorganic filler (C), a decane coupling agent (D), and zinc phosphate (E). The rubber composition of claim 1, wherein the inorganic filler (C) contains cerium oxide. The rubber composition of claim 1, wherein the inorganic filler (C) contains carbon black. The rubber composition according to claim 1 is the amine hydrazine derivative (A), the natural rubber and/or the synthetic rubber (B), the inorganic filler (C), and the decane coupling agent. (D) and the zinc phosphate (E) are obtained by mixing at 20 to 180 °C. The rubber composition of the first aspect of the invention, wherein the content of the zinc phosphate (E) is 0.01 to 10 parts by mass based on 100 parts by mass of the natural rubber and/or the synthetic rubber (B). The rubber composition of the first aspect of the invention, wherein the content of the amine-based anthracene derivative (A) is 0.01 to 10 parts by mass based on 100 parts by mass of the natural rubber and/or the synthetic rubber (B). A tire comprising the rubber composition according to any one of claims 1 to 6 in the tread.